Core-shell particles, method for producing core-shell particles, and film

ABSTRACT

An object of the present invention is to provide a core shell particle having high luminous efficacy and a narrow emission half-width; a method of producing the same; and a film formed of the core shell particle. The core shell particle of the present invention includes: a core which contains a Group III element and a Group V element; a first shell which covers at least a part of a surface of the core; a second shell which covers at least a part of the first shell; and a coordination molecule in at least a part of an outermost surface, in which at least silicon is detected by X-ray photoelectron spectroscopy analysis, and a molar ratio of the silicon to the Group III element contained in the core, which is acquired by X-ray photoelectron spectroscopy analysis, is 3.1 or less.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of PCT International Application No.PCT/JP2017/040109 filed on Nov. 7, 2017, which claims priority under 35U.S.C. § 119(a) to Japanese Patent Application No. 2016-222142 filed onNov. 15, 2016. The above application is hereby expressly incorporated byreference, in its entirety, into the present application.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to a core shell particle, a method ofproducing the same, and a film containing a core shell particle.

2. Description of the Related Art

As semiconductor fine particles which are expected to be applied tocolloidal semiconductor nanoparticles (so-called quantum dots), GroupII-VI semiconductor fine particles or Group III-V semiconductor fineparticles have been known.

The particle diameter of these semiconductor fine particles is severalnanometers to several tens of nanometers.

Further, a band gap typically becomes larger as the particle diameter ofparticles having such a nanoscale decrease due to so-called quantum sizeeffects, and the emission characteristics in a wide wavelength band froma near infrared range to a visible light range can be controlled bycontrolling the particle size thereof.

Therefore, in order to use optical characteristics specific to thesemiconductor fine particles, applications to various devices such as aphotoelectric conversion element, an electronic device, a light-emittingelement, and a laser have been researched and developed.

After suggestion of a hot soap method (also referred to as a hotinjection method) which is a chemical synthesis method of quantum dotsin “Highly Luminescent InP/GaP/ZnS Nanocrystals and Their Application toWhite Light-Emitting Diodes”, Journal of the American Chemical Society134, written by S. Kim et al., 3804-3809 (2012), the research on quantumdots has been actively performed around the world.

Further, the examination of the quantum dots was performed mainly on aGroup II-VI semiconductor containing a Cd element or a Pb element at thetime of initial research, but the research on quantum dots which do notcontain Cd or Pb has been recently suggested since the Cd element andthe Pb element are substances regulated as Restriction on HazardousSubstances (Rohs) or the like (for example, JP5137825B).

SUMMARY OF THE INVENTION

The present inventors performed examination on core shell particleshaving multilayers of shell layers described in JP5137825B and “HighlyLuminescent InP/GaP/ZnS Nanocrystals and Their Application to WhiteLight-Emitting Diodes”, Journal of the American Chemical Society 134,written by S. Kim et al., 3804-3809 (2012), and it was found thatsynthesis conditions (for example, the reaction atmosphere, the reactiontemperature, and the reaction time) have not been established, and theluminous efficacy or the emission half-width significantly fluctuatesdepending on the synthesis conditions.

Accordingly, an object of the present invention is to provide a coreshell particle having high luminous efficacy and a narrow emissionhalf-width, a method of producing the same, and a film formed of thecore shell particle.

As a result of intensive examination conducted by the present inventorsin order to achieve the above-described object, it was found that, in acore shell particle including: a core which contains a Group III elementand a Group V element; a first shell which covers at least a part of asurface of the core; a second shell which covers at least a part of thefirst shell; and a coordination molecule in at least a part of anoutermost surface, the luminous efficacy is excellent and the emissionhalf-width becomes narrow in a case where at least silicon is detectedby X-ray photoelectron spectroscopy analysis, and a molar ratio of thesilicon to the Group III element contained in the core, which isacquired by X-ray photoelectron spectroscopy analysis, is 3.1 or less,thereby completing the present invention.

In other words, it was found that the above-described object can beachieved by the following configurations.

[1] A core shell particle comprising: a core which contains a Group IIIelement and a Group V element; a first shell which covers at least apart of a surface of the core; a second shell which covers at least apart of the first shell; and a coordination molecule in at least a partof an outermost surface, in which at least silicon is detected by X-rayphotoelectron spectroscopy analysis, and a molar ratio of the silicon tothe Group III element contained in the core, which is acquired by X-rayphotoelectron spectroscopy analysis, is 3.1 or less.

[2] The core shell particle according to [1], in which the molar ratioof the silicon to the Group III element contained in the core, which isacquired by X-ray photoelectron spectroscopy analysis, is 1.6 or less.

[3] The core shell particle according to [1], in which the molar ratioof the silicon to the Group III element contained in the core, which isacquired by X-ray photoelectron spectroscopy analysis, is 1.2 or less.

[4] The core shell particle according to any one of [1] to [3], in whichthe Group III element contained in the core is In, and the Group Velement contained in the core is any of P, N, or As.

[5] The core shell particle according to [4], in which the Group IIIelement contained in the core is In, and the Group V element containedin the core is P.

[6] The core shell particle according to any one of [1] to [5], in whichthe core further contains a Group II element.

[7] The core shell particle according to [6], in which the Group IIelement contained in the core is Zn.

[8] The core shell particle according to any one of [1] to [7], in whichthe first shell contains a Group II element or a Group III element,wherein, in a case where the first shell contains the Group III element,the Group III element contained in the first shell is a Group IIIelement which is different from the Group III element contained in thecore.

[9] The core shell particle according to any one of [1] to [8], in whichthe first shell is a Group II-VI semiconductor which contains a Group IIelement and a Group VI element or a Group III-V semiconductor whichcontains a Group III element and a Group V element, wherein, in a casewhere the first shell is the Group III-V semiconductor, the Group IIIelement contained in the Group III-V semiconductor is a Group IIIelement which is different from the Group III element contained in thecore.

[10] The core shell particle according to [9], in which, in a case wherethe first shell is the Group II-VI semiconductor, the Group II elementis Zn and the Group VI element is Se or S, and in a case where the firstshell is the Group III-V semiconductor, the Group III element is Ga andthe Group V element is P.

[11] The core shell particle according to [9], in which the first shellis the Group III-V semiconductor, the Group III element is Ga, and theGroup V element is P.

[12] The core shell particle according to any one of [1] to [11], inwhich the second shell is a Group II-VI semiconductor which contains aGroup II element and a Group VI element or a Group III-V semiconductorwhich contains a Group III element and a Group V element.

[13] The core shell particle according to [12], in which the secondshell is the Group II-VI semiconductor, the Group II element is Zn, andthe Group VI element is S.

[14] The core shell particle according to any one of [1] to [13], inwhich the core, the first shell, and the second shell each have acrystal system having a zinc blende structure.

[15] The core shell particle according to any one of [1] to [14], inwhich, among the core, the first shell, and the second shell, a band gapof the core is the smallest, and the core and the first shellrespectively have a type 1 band structure.

[16] A method of producing a core shell particle for synthesizing thecore shell particle according to any one of [1] to [15], the methodcomprising: a first step of heating and stirring a solution obtained byadding a Group III raw material which contains a Group III element to asolvent containing coordination molecules; a second step of forming acore by adding a solution to which a Group V raw material containing aGroup V element and silicon has been added to the solution after thefirst step; a third step of growing the core in the solution after thesecond step; a fourth step of forming a first shell by adding a rawmaterial of the first shell to the solution after the third step; and afifth step of forming a second shell by adding a raw material of thesecond shell to the solution after the fourth step and synthesizing acore shell particle, in which the second step is performed in an argongas atmosphere, the third step, the fourth step, and the fifth step areperformed in an inert gas atmosphere, and the third step is a step ofholding the state at a temperature of 150° C. or higher for 30 minutesor longer.

[17] A method of producing a core shell particle for synthesizing thecore shell particle according to any one of [1] to [15], the methodcomprising: a first step of heating and stirring a solution obtained byadding a Group III raw material which contains a Group III element to asolvent containing coordination molecules; a second step of forming acore by adding a solution to which a Group V raw material containing aGroup V element and silicon has been added to the solution after thefirst step; a third step of growing the core in the solution after thesecond step; a fourth step of forming a first shell by adding a rawmaterial of the first shell to the solution after the third step; and afifth step of forming a second shell by adding a raw material of thesecond shell to the solution after the fourth step and synthesizing acore shell particle, in which each of the second step to the fifth stepis performed in an inert gas atmosphere, and the third step is a step ofholding the state at a temperature of 200° C. or higher for longer than2 hours.

[18] The method of producing a core shell particle according to [17], inwhich the holding time in the third step is 150 minutes or longer.

[19] The method of producing a core shell particle according to [17], inwhich the holding time in the third step is 165 minutes or longer.

[20] The method of producing a core shell particle according to any oneof [17] to [19], in which the holding time in the third step is 300minutes or shorter.

[21] The method of producing a core shell particle according to any oneof [17] to [20], in which the holding temperature in the third step is250° C. or higher.

[22] The method of producing a core shell particle according to any oneof [17] to [21], in which the holding temperature in the third step is290° C. or lower.

[23] A film comprising: the core shell particle according to any one of[1] to [15].

According to the present invention, it is possible to provide a coreshell particle having high luminous efficacy and a narrow emissionhalf-width, a method of producing the same, and a film formed of thecore shell particle.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, the present invention will be described in detail.

The description of constituent elements below will be occasionally madebased on representative embodiments of the present invention, but thepresent invention is not limited to these embodiments.

In the present specification, the numerical ranges expressed using “to”indicate the ranges including the numerical values described before andafter “to” as the lower limits and the upper limits.

[Core Shell Particle]

A core shell particle according to the embodiment of the presentinvention includes a core which contains a Group III element and a GroupV element, a first shell which covers at least a part of a surface ofthe core, a second shell which covers at least a part of the firstshell, and a coordination molecule in at least a part of an outermostsurface.

Further, in the core shell particle according to the embodiment of thepresent invention, at least silicon is detected by X-ray photoelectronspectroscopy (hereinafter, also referred to as “XPS”) analysis, and themolar ratio of the silicon to the Group III element (hereinafter,referred to as the “molar ratio (silicon/Group III element)”) containedin the core, which is acquired by XPS analysis, is 3.1 or less.

Here, the above-described molar ratio is acquired in the followingmanner.

In other words, the molar ratio is acquired by performing measurement onthe core shell particles according to XPS and correcting the ratio ofthe peak intensity of the Group III element contained in the core to thepeak intensity of silicon elements contained in the entirety of the coreshell particles with a relative sensitivity coefficient for eachelement. The relative sensitivity coefficient is acquired by measuringmeasurement elements (measurement trajectory) described below related tostandard samples whose compositions have been known (Journal of SurfaceAnalysis, Vol. 12, No. 3, pp. 357 (2005)).

Further, the peak intensity indicates the area intensity obtained bysubtracting the background from the peak observed under the followingmeasurement conditions and integrating the area of the peak with respectto the energy.

Further, the XPS measurement is performed by using a sample obtained byadding dropwise a dispersion liquid (solvent: toluene) containing coreshell particles on a non-doped silicon substrate in a glove box anddrying the dispersion liquid.

<Measurement Conditions>

-   -   Measuring device: Quantera SXM type XPS (manufactured by        ULVAC-PHI, Inc.)    -   X-ray source: Al-Kα ray (analytic diameter: 100 μm, 25 W, 15 kV)    -   Extraction angle of photoelectrons: 45°    -   Measurement range: 300 μm×300 μm    -   Correction: charging correction using combination of electron        gun and low-speed ion gun    -   Measurement elements (measurement trajectory): C (1s), N (1s), O        (1s), Si (2p), P (2p), S (2p), Cl (2p), Zn (2p3/2), Ga (2p3/2),        In (3d5/2)

In the core shell particle according to the embodiment of the presentinvention, the luminous efficacy is increased and the emissionhalf-width is narrowed in a case where the molar ratio (silicon/GroupIII element) acquired by X-ray photoelectron spectroscopy analysis is3.1 or less.

The detailed reason why the luminous efficacy is increased and theemission half-width is narrowed is not clear, but is speculated asfollows.

First, the degradation of the emission half-width is assumed to becaused due to decomposition of raw materials, side reactions, and astate in which silicon remaining in the raw materials is taken into thecore during the production. Specifically, in a case where tetravalentsilicon is mixed into the core, it is considered that a crystalstructure of the core containing the Group III element and the Group Velement is in disorder by maintaining charge neutrality. Therefore, itis considered that disorder of the crystal structure causes unevennessof the effective particle diameter of the core particle and leads todegradation of the emission half-width.

In addition, degradation of the luminous efficacy is assumed to becaused by defects (defects at the interface between the core and theshell) in the surface of each core particle or defects of the surface ofthe shell. Specifically, in defect sites of the surface of the coreparticle and the surface of the shell, the luminous efficacy isconsidered to be degraded due to occurrence of non-radiativerecombination or a local increase in lattice mismatch.

Therefore, in the present invention, by setting the molar ratio(silicon/Group III element) to 3.1 or less, disorder of the crystalstructure of the core is suppressed so that the effective particlediameter of the core is made uniform, and thus a shell which is uniformand does not have any defect can be formed. Therefore, it is consideredthat the luminous efficacy is increased and the emission half-width isnarrowed.

In the present invention, from the viewpoint that the luminous efficacyis further increased and the emission half-width is further narrowed,the molar ratio (silicon/Group III element) is preferably 3.0 or less.From the viewpoint that the emission half-width is particularlynarrowed, the molar ratio is more preferably 1.6 or less and morepreferably 1.2 or less.

In the present invention, from the viewpoint that the emissionhalf-width is further narrowed, the proportion (hereinafter, alsoreferred to as an “silicon content ratio”) of silicon elements withrespect to the following measurement elements measured by the XPSanalysis under the above-described conditions is preferably 4% or less,more preferably 2% or less, and still more preferably 1.5% or less.

Here, the silicon content ratio is acquired by correcting the ratio ofthe peak intensity of silicon elements to a total peak intensity of thefollowing measurement elements contained in the entirety of the coreshell particles with a relative sensitivity coefficient for eachelement.

-   -   Measurement elements (measurement trajectory): C (1s), N (1s), O        (1s), Si (2p), P (2p), S (2p), Cl (2p), Zn (2p3/2), Ga (2p3/2),        In (3d5/2)

[Core]

The core contained in the core shell particle according to theembodiment of the present invention is a so-called Group III-Vsemiconductor that contains a Group III element and a Group V element.

<Group III Element>

Specific examples of the Group III element include indium (In), aluminum(Al), and gallium (Ga). Among these, In is preferable.

<Group V Element>

Specific examples of the Group V element include phosphorus (P),nitrogen (N), and arsenic (As). Among these, P is preferable.

In the present invention, a Group III-V semiconductor obtained byappropriately combining the Group III element and the Group V elementexemplified above can be used as the core, but InP, InN, or InAs ispreferable from the viewpoint that the luminous efficacy is furtherincreased, the emission half-width is narrowed, and a clear exciton peakis obtained. Among these, from the viewpoint of further increasing theluminous efficacy, InP is more preferable.

In the present invention, it is preferable that the core furthercontains a Group II element in addition to the Group III element and theGroup V element described above. Particularly in a case where the coreis InP, the lattice constant is decreased by doping Zn as the Group IIelement and the lattice matching performance with a shell (for example,GaP, ZnS, or the like described below) having a smaller lattice constantthan that of InP becomes excellent.

[First Shell]

The first shell contained in the core shell particle according to theembodiment of the present invention is a material that covers at least apart of the surface of the core.

Here, in the present invention, it is possible to confirm whether atleast a part of the surface of the core is covered with the first shellbased on composition distribution analysis according to energydispersive X-ray spectroscopy (TEM-EDX) using a transmission electronmicroscope.

In the present invention, from the viewpoint of easily suppressingdefects of the interface between the core and the first shell, it ispreferable that the first shell contains a Group II element or a GroupIII element.

Here, in a case where the first shell contains a Group III element, theGroup III element contained in the first shell is a Group III elementwhich is different from the Group III element contained in the coredescribed above.

Further, in addition to a Group II-VI semiconductor and a Group III-Vsemiconductor described below, a Group III-VI semiconductor (such asGa₂O₃ or Ga₂S₃) containing a Group III element and a Group VI element isexemplified as the first shell containing a Group II element or a GroupIII element.

In the present invention, from the viewpoint of obtaining an excellentcrystal phase with less defects, it is preferable that the first shellis a Group II-VI semiconductor containing a Group II element and a GroupVI element or a Group III-V semiconductor containing a Group III elementand a Group V element and more preferable that the first shell is aGroup III-V semiconductor in which a difference in lattice constantbetween the core described above and the first shell is small.

Here, in a case where the first shell is a Group III-V semiconductor,the Group III element contained in the Group III-V semiconductor is agroup III element which is different from the Group III elementcontained in the core described above.

<Group II-VI Semiconductor>

Specific examples of the Group II element contained in the Group II-VIsemiconductor include zinc (Zn), cadmium (Cd), and magnesium (Mg). Amongthese, Zn is preferable.

Further, specific examples of the Group VI element contained in theGroup II-VI semiconductor include sulfur (S), oxygen (O), selenium (Se),and tellurium (Te). Among these, S or Se is preferable and S is morepreferable.

A Group II-VI semiconductor obtained by appropriately combining theGroup II element and the Group VI element described above can be used asthe first shell, but it is preferable that the first shell has a crystalsystem (for example, a zinc blende structure) which is the same as orsimilar to the core described above. Specifically, ZnSe, ZnS, or a mixedcrystal of these is preferable and ZnSe is more preferable.

<Group III-V Semiconductor>

Specific examples of the Group III element contained in the Group III-Vsemiconductor include indium (In), aluminum (Al), and gallium (Ga).Among these, Ga is preferable. Further, as described above, the GroupIII element contained in the Group III-V semiconductor is a Group IIIelement which is different from the Group III element contained in thecore described above. For example, in a case where the Group III elementcontained in the core is In, the Group III element contained in theGroup III-V semiconductor is Al, Ga, or the like.

Further, specific examples of the Group V element contained in the GroupIII-V semiconductor include phosphorus (P), nitrogen (N), and arsenic(As). Among these, P is preferable.

A Group III-V semiconductor obtained by appropriately combining theGroup III element and the Group V element described above can be used asthe first shell, but it is preferable that the first shell has a crystalsystem (for example, a zinc blende structure) which is the same as orsimilar to the core described above. Specifically, GaP is preferable.

In the present invention, from the viewpoint of reducing defects of thesurface of the core shell particle to be obtained, it is preferable thata difference in lattice constant between the above-described core andthe first shell is small. Specifically, the difference in latticeconstant between the above-described core and the first shell ispreferably 10% or less and more preferably 7.5% or less.

Specifically, in a case where the above-described core is InP, it ispreferable that the first shell is ZnSe (difference in lattice constant:3.4%) or GaP (difference in lattice constant: 7.1%) as described above.Particularly, it is more preferable that the first shell is the sameGroup III-V semiconductor as the core and is GaP from the viewpoint thata mixed crystal state can be easily made on the interface between thecore and the first shell.

In the present invention, in a case where the first shell is a GroupIII-V semiconductor, the first shell may contain or dope another element(for example, the Group II element or the Group VI element describedabove) within the range that does not affect the magnitude correlation(core<first shell) of the band gap between the core and the first shell.Similarly, in a case where the first shell is a Group II-VIsemiconductor, the first shell may contain or dope another element (forexample, the Group III element or the Group V element described above)within the range that does not affect the magnitude correlation(core<first shell) of the band gap between the core and the first shell.

[Second Shell]

The second shell contained in the core shell particle according to theembodiment of the present invention is a material that covers at least apart of the surface of the first shell described above.

Here, in the present invention, it is possible to confirm whether atleast a part of the surface of the first shell is covered with thesecond shell based on composition distribution analysis according toenergy dispersive X-ray spectroscopy (TEM-EDX) using a transmissionelectron microscope.

In the present invention, from the viewpoints of suppressing defects ofthe interface between the first shell and the second shell and obtainingan excellent crystal phase with less defects, it is preferable that thesecond shell is a Group II-VI semiconductor containing a Group IIelement and a Group VI element or a Group III-V semiconductor containinga Group III element and a Group V element. Further, from the viewpointsof high reactivity of the material itself and easily obtaining a shellwith excellent crystallinity, it is more preferable that the secondshell is a Group II-VI semiconductor.

Examples of the Group II element, the Group VI element, the Group IIIelement, and the Group V element include those described in the sectionof the first shell.

A Group II-VI semiconductor obtained by appropriately combining theGroup II element and the Group VI element described above can be used asthe second shell, but it is preferable that the second shell has acrystal system (for example, a zinc blende structure) which is the sameas or similar to the core described above. Specifically, ZnSe, ZnS, or amixed crystal of these is preferable and ZnS is more preferable.

A Group III-V semiconductor obtained by appropriately combining theGroup III element and the Group V element described above can be used asthe second shell, but it is preferable that the second shell has acrystal system (for example, a zinc blende structure) which is the sameas or similar to the core described above. Specifically, GaP ispreferable.

In the present invention, from the viewpoint of reducing defects of thesurface of the core shell particle to be obtained, it is preferable thata difference in lattice constant between the above-described first shelland the second shell is small. Specifically, it is preferable that thedifference in lattice constant between the above-described first shelland the second shell is 10% or less. Further, from the viewpoint offurther reducing lattice mismatch so that the luminous efficacy islikely to be increased, the lattice mismatch is desirably 4% or less andmore desirably 2% or less.

Specifically, in a case where the above-described first shell is GaP, itis preferable that the second shell is ZnSe (difference in latticeconstant: 3.8%) or ZnS (difference in lattice constant: 0.8%) asdescribed above and more preferable that the second shell is ZnS.

In the present invention, in a case where the second shell is a GroupII-VI semiconductor, the second shell may contain or dope anotherelement (for example, the Group III element or the Group V elementdescribed above) within the range that does not affect the magnitudecorrelation (core<second shell) of the band gap between the core and thesecond shell. Similarly, in a case where the second shell is a GroupIII-V semiconductor, the second shell may contain or dope anotherelement (for example, the Group II element or the Group VI elementdescribed above) within the range that does not affect the magnitudecorrelation (core<second shell) of the band gap between the core and thesecond shell.

In the present invention, from the viewpoint that epitaxial growthbecomes easy and defects of an interface between layers are easilysuppressed, it is preferable that each of the core, the first shell, andthe second shell described above has a crystal system having a zincblende structure.

In the present invention, from the viewpoint that the probability ofexcitons remaining in the core becomes higher and the luminous efficacyis further increased, it is preferable that the band gap of the corefrom among the core, the first shell, and the second shell describedabove is the smallest and the core and the first shell are core shellparticles having a type 1 (type I) band structure.

[Coordination Molecule]

From the viewpoint of imparting dispersibility, it is desirable that theoutermost surface of the core shell particle according to the embodimentof the present invention has coordination molecules.

From the viewpoint of the dispersibility or the like in a solvent, it ispreferable that the coordination molecule contains aliphatichydrocarbon.

Further, from the viewpoint of improving the dispersibility, it ispreferable that the coordination molecule is a ligand having at least 6carbon atoms in the main chain and more preferable that the coordinationmolecule is a ligand having 10 or more carbon atoms in the main chain.

Such a coordination molecule is a saturated compound or an unsaturatedcompound, and specific examples thereof include decanoic acid, lauricacid, myristic acid, palmitic acid, stearic acid, behenic acid, oleicacid, erucic acid, oleylamine, dodecylamine, dodecanethiol,1,2-hexadecanethiol, trioctylphosphine oxide, and cetrimonium bromide.These may be used alone or in combination of two or more kinds thereof.

[Average Particle Diameter]

From the viewpoints of easily synthesizing particles having a uniformsize and easily controlling the emission wavelength using quantum sizeeffects, the average particle diameter of the core shell particlesaccording to the embodiment of the present invention is preferably 2 nmor greater. Further, from the viewpoint of holding high dispersibilityin a solution, the average particle diameter thereof is more preferably10 nm or less.

Here, the average particle diameter is a value obtained by directlyobserving at least 20 particles using a transmission electronmicroscope, calculating the diameters of circles having the same area asthe projected area of the particles, and arithmetically averaging thesevalues.

[First Method of Producing Core Shell Particles]

A first method of producing a core shell particle for synthesizing thecore shell particle according to the embodiment of the present inventiondescribed above (hereinafter, also referred to as the “first productionmethod of the present invention”) includes a first step of heating andstirring a solution obtained by adding a Group III raw material whichcontains a Group III element to a solvent containing coordinationmolecules; a second step of forming a core by adding a solution to whicha Group V raw material containing a Group V element and silicon has beenadded to the solution after the first step; a third step of growing thecore in the solution after the second step; a fourth step of forming afirst shell by adding a raw material of the first shell to the solutionafter the third step; and a fifth step of forming a second shell byadding a raw material of the second shell to the solution after thefourth step and synthesizing a core shell particle, in which the secondstep is performed in an argon gas atmosphere, the third step, the fourthstep, and the fifth step are performed in an inert gas atmosphere, andthe third step is a step of holding the state at a temperature of 150°C. or higher for 30 minutes or longer.

Here, examples of the Group III element and the Group V element are thesame as those described in the section of the core shell particleaccording to the embodiment of the present invention described above.

Hereinafter, raw materials and conditions of each treatment step will bedescribed in detail.

[First Step]

The first step included in the first production method of the presentinvention is a step of heating and stirring a solution obtained byadding a Group III raw material which contains a Group III element to asolvent containing coordination molecules.

<Coordination Molecule>

Examples of the coordination molecule used in the first step are thesame as those described in the section of the core shell particleaccording to the embodiment of the present invention described above.Among those, from the viewpoints of promoting the synthesis of the coreand having an appropriate coordination force with respect to the core,oleic acid, palmitic acid, and stearic acid are preferable.

<Solvent>

Preferred examples of the solvent used in the first step includenon-polar solvents having a boiling point of 170° C. or higher.

Examples of the non-polar solvents include aliphatic saturatedhydrocarbon such as n-decane, n-dodecane, n-hexanedecane, orn-octadecane; aliphatic unsaturated hydrocarbon such as 1-undecene,1-dodecene, 1-hexadecene, or 1-octadecene; and trioctylphosphine.

Among these, aliphatic unsaturated hydrocarbon having 12 or greatercarbon atoms is preferable and 1-octadecene is more preferable.

<Group III Raw Material>

Specific examples of the Group III raw material to be added to thesolvent containing the coordination molecule described above includeindium acetate, indium chloride, indium oxide, indium nitrate, indiumsulfate, and indium acid; aluminum phosphate, aluminum acetylacetonate,aluminum chloride, aluminum fluoride, aluminum oxide, aluminum nitrate,and aluminum sulfate; and gallium acetylacetonate, gallium chloride,gallium fluoride, gallium oxide, gallium nitrate, and gallium sulfate.

Among these, from the viewpoints of further improving the luminousefficacy and easily controlling the emission wavelength in a visiblerange, a compound containing In is preferable. Particularly, from theviewpoint that impurity ions such as a chloride are unlikely to be takeninto the core and excellent crystallinity is easily realized, it is morepreferable to use indium acetate.

Further, the Group III raw material containing a Group III element maybe used in plural kinds or may separately contain a metal compound.

<Group II Raw Material>

In the production method according to the embodiment of the presentinvention, a Group II raw material containing a Group II element may beadded together with the Group III raw material described above duringthe first step.

Specific examples of the Group II raw material including a Group IIelement include dimethyl zinc, diethyl zinc, zinc carboxylate, zincacetylacetonate, zinc iodide, zinc bromide, zinc chloride, zincfluoride, zinc carbonate, zinc cyanide, zinc nitrate, zinc oxide, zincperoxide, zinc perchlorate, zinc acetate, and zinc sulfate.

Among these, from the viewpoints that impurities such as a chloride arenot contained and the compatibility with the coordination moleculedescribed above and the solubility in a solvent are relatively high, itis preferable to use zinc acetate, which is an acetate of Zn.

<Conditions for Heating and Stirring Solution>

In the first step, it is preferable that the coordination molecules andthe Group III raw material described above are dissolved in the solventdescribed above and also preferable that the coordination molecules andthe Group III raw material are dissolved in the solvent by heating andstirring the solution in a temperature range of 100° C. to 180° C. Atthis time, it is preferable that dissolved oxygen or moisture is removedfrom the mixed solution, in which the coordination molecules and theGroup III raw material have been dissolved, by heating the solutionunder reduced pressure.

Further, the time required for heating and dissolving is preferably 30minutes or longer.

In the first production method of the present invention, from theviewpoints of easily forming a uniform core in the second step describedbelow and improving the crystallinity of the formed core, it ispreferable that the first step is carried out by increasing thetemperature to a range of 230° C. to 310° C. after the solution isheated and stirred.

Further, in order to reduce the influence of oxygen dissolved in thesolution at the start of the second step described below, it ispreferable that the step of increasing the temperature after thesolution is heated and stirred is performed in an argon gas atmosphere.Further, the purity of the argon gas is preferably 99.999% by volume orgreater.

[Second Step]

The second step included in the first production method of the presentinvention is a step of forming a core by adding a solution to which aGroup V raw material containing a Group V element and silicon has beenadded to the solution after the first step in an argon gas atmosphere.

<Group V Raw Material>

As a Group V raw material containing a Group V element and silicon (Si),for example, a raw material containing phosphorus (P) as the Group Velement is preferable, and specific examples thereof include compoundscontaining P and Si, such as alkylsilylphosphine, alkylsilylphosphineoxide, allylsilylphosphine, and allylsilylphosphine oxide.

Among these, alkylsilylphosphine is preferable from the viewpoint offurther improving the reactivity with a Group III raw material.

Examples of alkylsilylphosphine include tristrialkylsilylphosphine andtrisdialkylsilylphosphine, and specific preferred examples thereofinclude tristrimethylsilylphosphine.

Further, the Group V raw material containing a Group V element andsilicon may be used in plural kinds or may separately contain a metalcompound.

<Group II Raw Material>

According to the production method according to the embodiment of thepresent invention, a Group II raw material containing a Group II elementmay be added together with the above-described Group V raw material inthe second step.

Specific examples of the Group II raw material containing a Group IIelement are the same as those described as the optional raw materials ofthe first step above.

[Third Step]

The third step included in the first production method of the presentinvention is a step of growing the core in the solution after the secondstep in an inert gas atmosphere and holding the state at a temperatureof 150° C. or higher for 30 minutes or longer. Here, examples of theinert gas include argon gas and nitrogen gas.

<Conditions for Growing Core>

The holding temperature in the third step is 150° C. or higher asdescribed above, but is preferably 200° C. or higher from the viewpointsof improving the crystallinity of the particles and further reducingimpurities. Further, since new nucleation of particles, excessive growthof particles, Ostwald ripening, and the like are suppressed so that theuniformity of the particle size is improved, the holding temperature ispreferably 290° C. or lower and more preferably lower than 290° C.

Further, the holding time in the third step is 30 minutes or longer asdescribed above, but is preferably 60 minutes or longer, more preferably120 minutes or longer, and still more preferably 150 minutes or longerfrom the viewpoints of improving the crystallinity of the particles andfurther reducing impurities. Further, since new nucleation of particles,excessive growth of particles, Ostwald ripening, and the like aresuppressed so that the uniformity of the particle size is improved, theholding time is preferably 300 minutes or shorter and more preferablyshorter than 300 minutes.

[Fourth Step]

The fourth step included in the first production method of the presentinvention is a step of forming a first shell by adding a raw material ofthe first shell to the solution after the third step in an inert gasatmosphere.

Here, examples of the inert gas include argon gas and nitrogen gas.

Further, as the raw material of the first shell, a Group II raw materialcontaining the Group II element described above and a Group VI rawmaterial containing the Group VI element described below are exemplifiedin a case where the first shell is the Group II-VI semiconductordescribed above; and a Group III raw material containing the Group IIIelement described above and a Group V raw material containing the GroupV element described above are exemplified in a case where the firstshell is the Group III-V semiconductor described above.

Here, in a case where the first shell is the above-described Group III-Vsemiconductor, as described in the section of the core shell particleaccording to the embodiment of the present invention, the Group IIIelement contained in the Group III-V semiconductor is a Group IIIelement which is different from the Group III element contained in thecore described above.

Further, in a case where the first shell is the Group III-Vsemiconductor described above, since the Group V raw material containinga Group V element is the same raw material as the Group V raw materialforming the core, a part of the Group V raw material used in the secondstep may be used and only the Group III raw material may be added in thefourth step.

<Group VI Raw Material>

Specific examples of the Group VI raw material containing a Group VIelement include sulfur, alkylthiol, trialkylphosphine sulfide,trialkenylphosphine sulfide, alkylamino sulfide, alkenylamino sulfide,cyclohexyl isothiocyanate, dialkyl dithiocarbamic acid, and diethyldithiocarbamic acid; and trialkylphosphine selenium, trialkenylphosphineselenium, alkylamino selenium, alkenylamino selenium, trialkylphosphinetelluride, trialkenylphosphine telluride, alkylamino telluride, andalkenylamino telluride.

Among these, from the viewpoint of excellent dispersibility of coreshell particles to be obtained, it is preferable to use alkylthiol,specifically, more preferable to use dodecanethiol or octanethiol, andstill more preferable to use dodecanethiol.

Among these materials, it is preferable to use the Group III rawmaterial and the Group V raw material.

Particularly, as the Group III raw material, it is more preferable touse a compound containing Ga (such as gallium acetylacetonate, galliumchloride, gallium fluoride, gallium oxide, gallium nitrate, or galliumsulfate) and still more preferable to use a chloride of Ga.

In addition, as the Group V raw material, it is preferable to use a partof the Group V raw material used in the second step as described above.

[Fifth Step]

The fifth step included in the first production method of the presentinvention is a step of synthesizing a core shell particle by adding araw material of a second shell to the solution after the fourth step inan inert gas atmosphere to form the second shell.

Further, examples of the inert gas include argon gas and nitrogen gas.

Here, as the raw material of the second shell, a Group II raw materialcontaining the Group II element described above and a Group VI rawmaterial containing the Group VI element described above are exemplifiedin a case where the second shell is the Group II-VI semiconductordescribed above; and a Group III raw material containing the Group IIIelement described above and a Group V raw material containing the GroupV element described above are exemplified in a case where the secondshell is the Group III-V semiconductor described above.

Among these raw materials, it is preferable to use the Group II rawmaterial and the Group VI raw material.

Particularly, it is preferable to use a compound containing Zn(particularly, a carboxylate of Zn) as the Group II raw material.

Further, it is preferable to use alkylthiol as the Group VI rawmaterial.

[Second Method of Producing Core Shell Particles]

A second method of producing a core shell particle for synthesizing thecore shell particle according to the embodiment of the present inventiondescribed above (hereinafter, also referred to as the “second productionmethod of the present invention”) includes a first step of heating andstirring a solution obtained by adding a Group III raw material whichcontains a Group III element to a solvent containing coordinationmolecules; a second step of forming a core by adding a solution to whicha Group V raw material containing a Group V element and silicon has beenadded to the solution after the first step; a third step of growing thecore in the solution after the second step; a fourth step of forming afirst shell by adding a raw material of the first shell to the solutionafter the third step; and a fifth step of forming a second shell byadding a raw material of the second shell to the solution after thefourth step and synthesizing a core shell particle, in which each of thesecond step to the fifth step is performed in an inert gas atmosphere,and the third step is a step of holding the state at a temperature of200° C. or higher for longer than 2 hours.

Here, examples of the Group III element and the Group V element are thesame as those described in the section of the core shell particleaccording to the embodiment of the present invention described above.

Hereinafter, raw materials and conditions of each treatment step will bedescribed in detail.

[First Step]

The first step included in the second production method of the presentinvention is a step of heating and stirring a solution obtained byadding a Group III raw material which contains a Group III element to asolvent containing coordination molecules in the same manner as in thefirst step included in the first production method of the presentinvention.

<Coordination Molecule>

Examples of the coordination molecule used in the first step include thesame coordination molecules as those used in the first step included inthe first production method of the present invention.

<Solvent>

Examples of the solvent used in the first step include the same solventsas those used in the first step included in the first production methodof the present invention.

<Group III Raw Material>

Examples of the Group III raw material to be added to the solventcontaining the coordination molecule described above include the sameGroup III raw materials as those used in the first step included in thefirst production method of the present invention.

<Group II Raw Material>

In the production method according to the embodiment of the presentinvention, a Group II raw material containing a Group II element may beadded together with the Group III raw material described above duringthe first step.

Examples of the Group II raw material containing a Group II elementinclude the same Group II raw materials as those used in the first stepincluded in the first production method of the present invention.

<Conditions for Heating and Stirring Solution>

In the first step, it is preferable that the coordination molecules andthe Group III raw material described above are dissolved in the solventdescribed above and also preferable that the coordination molecules andthe Group III raw material are dissolved in the solvent by heating andstirring the solution in a temperature range of 100° C. to 180° C. Atthis time, it is preferable that dissolved oxygen or moisture is removedfrom the mixed solution, in which the coordination molecules and theGroup III raw material have been dissolved, by heating the solutionunder reduced pressure.

Further, the time required for heating and dissolving is preferably 30minutes or longer.

In the second production method of the present invention, from theviewpoints of easily forming a uniform core in the second step describedbelow and improving the crystallinity of the formed core, it ispreferable that the first step is carried out by increasing thetemperature to a range of 230° C. to 310° C. after the solution isheated and stirred.

Further, in order to reduce the influence of oxygen dissolved in thesolution at the start of the second step described below, it ispreferable that the step of increasing the temperature after thesolution is heated and stirred is performed in an argon gas atmosphere.Further, the purity of the argon gas is preferably 99.999% by volume orgreater.

[Second Step]

The second step included in the second production method of the presentinvention is a step of forming a core by adding a solution to which aGroup V raw material containing a Group V element and silicon has beenadded to the solution after the first step in an inert gas atmosphere.Here, examples of the inert gas include argon gas and nitrogen gas.

<Group V Raw Material>

As the Group V raw material containing a Group V element and silicon,the same Group V raw materials as those used in the second step includedin the first production method of the present invention are preferablyused.

<Group II Raw Material>

According to the production method according to the embodiment of thepresent invention, a Group II raw material containing a Group II elementmay be added together with the above-described Group V raw material inthe second step.

Specific examples of the Group II raw material containing a Group IIelement are the same as those described as the optional raw materials ofthe first step above.

[Third Step]

The third step included in the second production method of the presentinvention is a step of growing the core in the solution after the secondstep in an inert gas atmosphere and holding the state at a temperatureof 200° C. or higher for 2 hours or longer. Here, examples of the inertgas include argon gas and nitrogen gas.

<Conditions for Growing Core>

The holding temperature in the third step is 200° C. or higher asdescribed above, but is preferably 250° C. or higher from the viewpointsof improving the crystallinity of the particles and further reducingimpurities. Further, since new nucleation of particles, excessive growthof particles, Ostwald ripening, and the like are suppressed so that theuniformity of the particle size is improved, the holding temperature ispreferably 290° C. or lower.

Further, the holding time in the third step is longer than 2 hours asdescribed above, but is preferably 150 minutes or longer and morepreferably 165 minutes or longer from the viewpoints of improving thecrystallinity of the particles and further reducing impurities. Further,since new nucleation of particles, excessive growth of particles,Ostwald ripening, and the like are suppressed so that the uniformity ofthe particle size is improved, the holding time is preferably 300minutes or shorter.

[Fourth Step]

The fourth step included in the second production method of the presentinvention is a step of forming a first shell by adding a raw material ofthe first shell to the solution after the third step in an inert gasatmosphere in the same manner as in the first step included in the firstproduction method of the present invention.

Here, examples of the inert gas include argon gas and nitrogen gas.

As the raw material of the first shell, the same raw materials as thoseused in the fourth step included in the first production method of thepresent invention are preferably used.

<Group VI Raw Material>

As the Group VI raw material containing a Group VI element, the sameGroup VI raw materials as those used in the fourth step included in thefirst production method of the present invention are preferably used.

[Fifth Step]

The fifth step included in the second production method of the presentinvention is a step of synthesizing a core shell particle by adding araw material of a second shell to the solution after the third step inan inert gas atmosphere to form the second shell in the same manner asin the fifth step included in the first production method of the presentinvention.

Further, examples of the inert gas include argon gas and nitrogen gas.

As the raw material of the second shell, the same raw materials as thoseused in the first step included in the first production method of thepresent invention are preferably used.

[Film]

The film according to the embodiment of the present invention is a filmcontaining the core shell particle according to the embodiment of thepresent invention described above.

Since such a film according to the embodiment of the present inventionhas high luminous efficacy and a narrowed emission half-width and isuseful as quantum dots, the film can be applied to a wavelengthconversion film used for a display, a photoelectron conversion (orwavelength conversion) film of a solar cell, a biological label, a thinfilm transistor, and the like. Particularly, the film according to theembodiment of the present invention is suitably applied to a downconversion film or a down shift type wavelength conversion film whichabsorbs light in a shorter wave region than that of the absorption edgeof quantum dots and emits light having a long wave.

Further, the film material as a base material constituting the filmaccording to the embodiment of the present invention is not particularlylimited and may be a resin or a thin glass film.

Specific examples thereof include resin materials formed of an ionomer,polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinylalcohol, polyamide, polylactic acid, polyurethane,polytetrafluoroethylene, polyacetal, polypropylene, polyester,polycarbonate, polystyrene, polyacrylonitrile, an ethylene vinyl acetatecopolymer, an ethylene-vinyl alcohol copolymer, an ethylene-methacrylicacid copolymer film, an acrylic resin, or nylon.

EXAMPLES

Hereinafter, the present invention will be described in more detailbased on examples. The materials, the use amounts, the ratios, thetreatment contents, and the treatment procedures described in thefollowing examples can be changed as appropriate within the range notdeparting from the gist of the present invention. Therefore, the scopeof the present invention should not be limitatively interpreted by thefollowing examples.

Example 1

32 mL of octadecene, 140 mg (0.48 mmol) of indium acetate, 48 mg (0.26mmol) of zinc acetate, and 485 mg (1.89 mmol) of palmitic acid wereadded to a flask, heated and stirred at 110° C. in a vacuum, anddegassed while the raw materials were sufficiently dissolved.Thereafter, the flask was heated to 300° C. in an argon flow, and thetemperature of the solution was stabilized (first step).

Next, 0.18 mmol of tristrimethylsilylphosphine dissolved inapproximately 4 mL of octadecene was added to the flask in the argon gasflow, and the state in which the solution was colored in red andparticles (cores) were formed was confirmed (second step).

Thereafter, the flask was heated for 120 minutes in a state in which thetemperature of the solution was held at 230° C. in the argon gas flow,and the cores were allowed to grow (third step).

Next, 30 mg (0.18 mmol) of gallium chloride and 188 μL (0.6 mmol) ofoleic acid which were dissolved in 8 mL of octadecene were added to thesolution in a state in which the solution was heated to 200° C. in theargon gas flow, and the solution was further heated for approximately 1hour, thereby obtaining a dispersion liquid of a core shell particleprecursor including InP (core) doped with Zn and GaP (first shell)(fourth step).

Next, the dispersion liquid was cooled to room temperature, 0.93 mmol ofzinc oleate was added thereto, the dispersion liquid was heated to 240°C. in the argon gas flow, and the state thereof was held forapproximately 4 hours. Next, 0.55 mL (2.3 mmol) of dodecanethiol wasadded to the dispersion liquid and the state of the resulting dispersionliquid was held for approximately 2 hours in the argon gas flow, therebyobtaining a dispersion liquid of a core shell particle including InP(core) doped with Zn, GaP (first shell) covering the surface of thecore, and ZnS (second shell) covering the surface of the first shell(fifth step).

The obtained dispersion liquid was cooled to room temperature, and theargon gas flow was stopped. Thereafter, ethanol was added to thedispersion liquid, and centrifugation was performed on the dispersionliquid so that particles were precipitated. The supernatant was disposedof and the resultant was allowed to be dispersed in a toluene solvent.In this manner, a toluene dispersion liquid of a core shell particleincluding InP (core) doped with Zn, GaP (first shell) covering thesurface of the core, and ZnS (second shell) covering the surface of thefirst shell, was obtained.

Examples 2 and 3

Samples were synthesized in the same process as in Example 1 except thatthe third step was performed under changed conditions as listed in Table1 below.

Example 4

32 mL of octadecene, 140 mg (0.48 mmol) of indium acetate, 48 mg (0.26mmol) of zinc acetate, and 485 mg (1.89 mmol) of palmitic acid wereadded to a flask, heated and stirred at 110° C. in a vacuum, anddegassed while the raw materials were sufficiently dissolved.Thereafter, the flask was heated to 300° C. in a nitrogen gas flow, andthe temperature of the solution was stabilized (first step).

Next, 0.18 mmol of tristrimethylsilylphosphine dissolved inapproximately 4 mL of octadecene was added to the flask in the nitrogengas flow, and the state in which the solution was colored in red andparticles (cores) were formed was confirmed (second step).

Thereafter, the flask was heated for 150 minutes in a state in which thetemperature of the solution was held at 230° C. in the nitrogen gasflow, and the cores were allowed to grow (third step).

Next, 30 mg (0.18 mmol) of gallium chloride and 188 μL (0.6 mmol) ofoleic acid which were dissolved in 8 mL of octadecene were added to thesolution in a state in which the solution was heated to 200° C. in thenitrogen gas flow, and the solution was further heated for approximately1 hour, thereby obtaining a dispersion liquid of a core shell particleprecursor including InP (core) doped with Zn and GaP (first shell)(fourth step).

Next, the dispersion liquid was cooled to room temperature, 0.93 mmol ofzinc oleate was added thereto, the dispersion liquid was heated to 240°C. in the nitrogen gas flow, and the state thereof was held forapproximately 4 hours. Next, 0.55 mL (2.3 mmol) of dodecanethiol wasadded to the dispersion liquid and the state of the resulting dispersionliquid was held for approximately 2 hours in the nitrogen gas flow,thereby obtaining a dispersion liquid of a core shell particle includingInP (core) doped with Zn, GaP (first shell) covering the surface of thecore, and ZnS (second shell) covering the surface of the first shell(fifth step).

The obtained dispersion liquid was cooled to room temperature, and thenitrogen gas flow was stopped. Thereafter, ethanol was added to thedispersion liquid, and centrifugation was performed on the dispersionliquid so that particles were precipitated. The supernatant was disposedof and the resultant was allowed to be dispersed in a toluene solvent.In this manner, a toluene dispersion liquid of a core shell particleincluding InP (core) doped with Zn, GaP (first shell) covering thesurface of the core, and ZnS (second shell) covering the surface of thefirst shell, was obtained.

Examples 5 to 7

Samples were synthesized in the same process as in Example 4 except thatthe third step was performed under changed conditions as listed in Table1 below.

Comparative Example 1

32 mL of octadecene, 140 mg (0.48 mmol) of indium acetate, 48 mg (0.26mmol) of zinc acetate, and 364 mg (1.44 mmol) of palmitic acid wereadded to a flask, heated and stirred at 110° C. in a vacuum, anddegassed while the raw materials were sufficiently dissolved.Thereafter, the flask was heated to 300° C. in a nitrogen gas flow, andthe temperature of the solution was stabilized (first step).

Next, 0.24 mmol of tristrimethylsilylphosphine dissolved inapproximately 4 mL of octadecene was added to the flask in the nitrogengas flow, and the state in which the solution was colored in red andparticles (cores) were formed was confirmed (second step).

Thereafter, the flask was heated for 120 minutes in a state in which thetemperature of the solution was held at 230° C. in the nitrogen gasflow, and the cores were allowed to grow in the same manner as in“Highly Luminescent InP/GaP/ZnS Nanocrystals and Their Application toWhite Light-Emitting Diodes”, Journal of the American Chemical Society134, written by S. Kim et al., 3804-3809 (2012) (third step).

Next, 20 mg (0.12 mmol) of gallium chloride and 125 μL (0.4 mmol) ofoleic acid which were dissolved in 8 mL of octadecene were added to thesolution in a state in which the solution was heated to 200° C. in thenitrogen gas flow, and the solution was further heated for approximately1 hour, thereby obtaining a dispersion liquid of a core shell particleprecursor including InP (core) doped with Zn and GaP (first shell)(fourth step).

Next, the dispersion liquid was cooled to room temperature, 220 mg (1.2mmol) of zinc acetate was added thereto, the dispersion liquid washeated to 230° C., and the state thereof was held for approximately 4hours. Next, 479 μL (2.0 mmol) of dodecanethiol was added to thedispersion liquid and the state of the resulting dispersion liquid washeld at 230° C. for approximately 2 hours in the nitrogen gas flow,thereby obtaining a dispersion liquid of a core shell particle includingInP (core) doped with Zn, GaP (first shell) covering the surface of thecore, and ZnS (second shell) covering the surface of the first shell(fifth step).

The obtained dispersion liquid was cooled to room temperature, and thenitrogen gas flow was stopped. Thereafter, ethanol was added to thedispersion liquid, and centrifugation was performed on the dispersionliquid so that particles were precipitated. The supernatant was disposedof and the resultant was allowed to be dispersed in a toluene solvent.In this manner, a toluene dispersion liquid of a core shell particleincluding InP (core) doped with Zn, GaP (first shell) covering thesurface of the core, and ZnS (second shell) covering the surface of thefirst shell, was obtained.

Comparative Examples 2 and 3

Samples were synthesized in the same process as in Example 4 except thatthe third step was performed under changed conditions as listed in Table1 below.

<Molar Ratio (Silicon/Group III Element)>

With the obtained core shell particles, the molar ratio [molar ratio(silicon/Group III element)] of silicon contained in the entirety of thecore shell particles to the Group III element contained in the core wasacquired by XPS. The details of the method of acquiring the molar ratio(silicon/Group III element) are as described above. The results arelisted in Table 1 below.

<Silicon Content Ratio>

With the obtained core shell particles, the proportion (silicon contentratio) of silicon elements with respect to the following measurementelements measured by the XPS analysis under the above-describedconditions was acquired. The details of the method of acquiring thesilicon content ratio are as described above. The results are listed inTable 1 below.

-   -   Measurement elements (measurement trajectory): C (1s), N (1s), O        (1s), Si (2p), P (2p), S (2p), Cl (2p), Zn (2p3/2), Ga (2p3/2),        In (3d5/2)

<Luminous Efficacy>

The emission intensity was measured by adjusting the concentration ofthe obtained dispersion liquid of the core shell particles such that theabsorbance at an excitation wavelength of 450 nm was set to 0.04 usingan absolute PL quantum yield measuring device C11347 (manufactured byHamamatsu Photonics K.K.). Further, the luminous efficacy was calculatedby performing relative comparison with a quantum dot sample whoseluminous efficacy was known. The obtained luminous efficacy wascalculated as a ratio of the number of emission photons to the number ofabsorption photons from excitation light. The results are listed inTable 1 below.

<Emission Half-Width>

With the obtained dispersion liquid of the core shell particles, thefluorescence spectrum was measured at room temperature using lighthaving an excitation wavelength of 450 nm to acquire the half-width.Specifically, each wavelength which becomes half of the peak intensityof the fluorescence spectrum to be observed was acquired, and theemission half-width was acquired from the difference in wavelength. Theresults are listed in Table 1 below.

TABLE 1 Third step Molar ratio Silicon Holding (silicon/ contentLuminous Emission Type of temperature Holding time Group III ratioefficacy half-width flow gas (° C.) (min) element) (%) (%) (nm) Example1 Argon 230 120 0.9 1.2 80.1 42 Example 2 Argon 190 150 1.5 1.9 77.6 47Example 3 Argon 230 150 0.8 1.1 81.2 41 Example 4 Nitrogen 230 150 1.41.8 78.4 48 Example 5 Nitrogen 230 165 1.0 1.3 79.8 43 Example 6Nitrogen 250 150 1.1 1.4 78.7 43 Example 7 Nitrogen 210 130 2.5 3.2 75.450 Example 8 Nitrogen 290 150 1.3 1.4 76.3 49 Example 9 Nitrogen 230 3001.3 1.5 77.3 49 Comparative Nitrogen 230 120 3.3 4.3 53.0 78 Example 1Comparative Nitrogen 190 150 3.2 4.2 75.2 58 Example 2 ComparativeNitrogen 230 100 3.3 4.1 76.2 56 Example 3

Based on the results listed in Table 1, it was found that the luminousefficacy was decreased and the emission half-width was widened in a caseof the core shell particles having a molar ratio (silicon/Group IIIelement) of greater than 3.1 (Comparative Examples 1 and 3).

Specifically, it was found that, in a case where the holding time forthe third step was 2 hours or shorter, similarly, the molar ratio(silicon/Group III element) was greater than 3.1, the luminous efficacywas decreased, and the emission half-width was widened (ComparativeExamples 1 and 3).

Further, it was found that, in a case where the holding temperature forthe third step was 200° C. or lower, the molar ratio (silicon/Group IIIelement) was greater than 3.1, the luminous efficacy was decreased, andthe emission half-width was widened (Comparative Example 2).

On the contrary, it was found that the luminous efficacy was increasedand the emission half-width was narrowed in a case of the core shellparticles having a molar ratio (silicon/Group III element) of 3.1 orless and containing cores, the first shells, the second shells, and thecoordination molecules (Examples 1 to 9).

Particularly, based on the comparison between Examples 4 to 7, it wasfound that the luminous efficacy was more increased and the emissionhalf-width was more narrowed in a case where the molar ratio(silicon/Group III element) was 1.6 or less, and the luminous efficacywas still more increased and the emission half-width was still morenarrowed in a case where the molar ratio (silicon/Group III element) was1.2 or less.

What is claimed is:
 1. A core shell particle comprising: a core whichcontains a Group III element and a Group V element; a first shell whichcovers at least a part of a surface of the core; a second shell whichcovers at least a part of the first shell; and a coordination moleculein at least a part of an outermost surface, wherein at least silicon isdetected by X-ray photoelectron spectroscopy analysis, and a molar ratioof the silicon to the Group III element contained in the core, which isacquired by X-ray photoelectron spectroscopy analysis, is 3.1 or less.2. The core shell particle according to claim 1, wherein the molar ratioof the silicon to the Group III element contained in the core, which isacquired by X-ray photoelectron spectroscopy analysis, is 1.6 or less.3. The core shell particle according to claim 1, wherein the molar ratioof the silicon to the Group III element contained in the core, which isacquired by X-ray photoelectron spectroscopy analysis, is 1.2 or less.4. The core shell particle according to claim 1, wherein the Group IIIelement contained in the core is In, and the Group V element containedin the core is any of P, N, or As.
 5. The core shell particle accordingto claim 4, wherein the Group III element contained in the core is In,and the Group V element contained in the core is P.
 6. The core shellparticle according to claim 1, wherein the core further contains a GroupII element.
 7. The core shell particle according to claim 6, wherein theGroup II element contained in the core is Zn.
 8. The core shell particleaccording to claim 1, wherein the first shell contains a Group IIelement or a Group III element, wherein, in a case where the first shellcontains the Group III element, the Group III element contained in thefirst shell is a Group III element which is different from the Group IIIelement contained in the core.
 9. The core shell particle according toclaim 1, wherein the first shell is a Group II-VI semiconductor whichcontains a Group II element and a Group VI element or a Group III-Vsemiconductor which contains a Group III element and a Group V element,wherein, in a case where the first shell is the Group III-Vsemiconductor, the Group III element contained in the Group III-Vsemiconductor is a Group III element which is different from the GroupIII element contained in the core.
 10. The core shell particle accordingto claim 9, wherein, in a case where the first shell is the Group II-VIsemiconductor, the Group II element is Zn and the Group VI element is Seor S, and in a case where the first shell is the Group III-Vsemiconductor, the Group III element is Ga and the Group V element is P.11. The core shell particle according to claim 9, wherein the firstshell is the Group III-V semiconductor, the Group III element is Ga, andthe Group V element is P.
 12. The core shell particle according to claim1, wherein the second shell is a Group II-VI semiconductor whichcontains a Group II element and a Group VI element or a Group III-Vsemiconductor which contains a Group III element and a Group V element.13. The core shell particle according to claim 12, wherein the secondshell is the Group II-VI semiconductor, the Group II element is Zn, andthe Group VI element is S.
 14. The core shell particle according toclaim 1, wherein the core, the first shell, and the second shell eachhave a crystal system having a zinc blende structure.
 15. The core shellparticle according to claim 1, wherein, among the core, the first shell,and the second shell, a band gap of the core is the smallest, and thecore and the first shell respectively have a type 1 band structure. 16.A method of producing a core shell particle for synthesizing the coreshell particle according to claim 1, the method comprising: a first stepof heating and stirring a solution obtained by adding a Group III rawmaterial which contains a Group III element to a solvent containingcoordination molecules; a second step of forming a core by adding asolution to which a Group V raw material containing a Group V elementand silicon has been added to the solution after the first step; a thirdstep of growing the core in the solution after the second step; a fourthstep of forming a first shell by adding a raw material of the firstshell to the solution after the third step; and a fifth step of forminga second shell by adding a raw material of the second shell to thesolution after the fourth step and synthesizing a core shell particle,wherein the second step is performed in an argon gas atmosphere, thethird step, the fourth step, and the fifth step are performed in aninert gas atmosphere, and the third step is a step of holding the stateat a temperature of 150° C. or higher for 30 minutes or longer.
 17. Amethod of producing a core shell particle for synthesizing the coreshell particle according to claim 1, the method comprising: a first stepof heating and stirring a solution obtained by adding a Group III rawmaterial which contains a Group III element to a solvent containingcoordination molecules; a second step of forming a core by adding asolution to which a Group V raw material containing a Group V elementand silicon has been added to the solution after the first step; a thirdstep of growing the core in the solution after the second step; a fourthstep of forming a first shell by adding a raw material of the firstshell to the solution after the third step; and a fifth step of forminga second shell by adding a raw material of the second shell to thesolution after the fourth step and synthesizing a core shell particle,wherein each of the second step to the fifth step is performed in aninert gas atmosphere, and the third step is a step of holding the stateat a temperature of 200° C. or higher for longer than 2 hours.
 18. Themethod of producing a core shell particle according to claim 17, whereinthe holding time in the third step is 150 minutes or longer.
 19. Themethod of producing a core shell particle according to claim 17, whereinthe holding time in the third step is 165 minutes or longer.
 20. Themethod of producing a core shell particle according to claim 17, whereinthe holding time in the third step is 300 minutes or shorter.
 21. Themethod of producing a core shell particle according to claim 17, whereinthe holding temperature in the third step is 250° C. or higher.
 22. Themethod of producing a core shell particle according to claim 17, whereinthe holding temperature in the third step is 290° C. or lower.
 23. Afilm comprising: the core shell particle according to claim 1.